Diisopropylamine → 1,1'-Undecane-1,11-diyldicyclopropanecarbonitrile

HRID 467991Notes

Reaction equation

HRID 467991 reaction equation
[CH2:1]([Li])[CH2:2][CH2:3][CH3:4].CCCCCC.[CH:12]([NH:15]C(C)C)(C)C.CN1C(=O)N(C)CCC1.[CH:28]1([C:31]#[N:32])[CH2:30][CH2:29]1.BrC[CH2:35][CH2:36][CH2:37][CH2:38][CH2:39][CH2:40][CH2:41][CH2:42][CH2:43][CH2:44]Br>C1COCC1>[CH2:1]([C:28]1([C:31]#[N:32])[CH2:30][CH2:29]1)[CH2:2][CH2:3][CH2:4][CH2:44][CH2:43][CH2:42][CH2:41][CH2:40][CH2:39][CH2:38][C:37]1([C:12]#[N:15])[CH2:36][CH2:35]1

Participants

8

Reactant 6

HCID 7912DiisopropylamineHCID 8058HexaneHCID 79637CyclopropanecarbonitrileHCID 816462(1H)-Pyrimidinone, tetrahydro-1,3-dimethyl-HCID 855511,11-DibromoundecaneHCID 178418339Butyllithium

Product 1

HCID 667955381,1'-Undecane-1,11-diyldicyclopropanecarbonitrileYield 68.5%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
-20 °C

Procedure

A solution of n-butyl lithium in hexane (1.8M, 297 mL, 0.53 mol) was added drop wise to a solution of freshly distilled diisopropylamine (78.3 mL, 0.50 mol) in dry THF (400 mL) at −60° C. under nitrogen atmosphere. The reaction mixture was slowly warmed to −20° C. and stirred for 30 min. The reaction mixture was re-cooled to −78° C., DMPU (8.16 g, 0.06 mol) was added drop wise and stirred for 15 min. Then cyclopropane carbonitrile (34.17 g, 0.50 mol) was added drop wise over a period 30 min and stirred for 1 h. To the reaction mixture was added drop wise 1,11-dibromoundecane (40.0 g, 0.12 mol) in dry THF (40 mL) and continued stirring at −78° C. for 2 h. The reaction mixture was slowly allowed to reach room temperature and continued stirring over a period of 16 h. The resulting reaction mixture was quenched with saturated NH4Cl (1.0 L) at 0° C. and the reaction mixture was extracted with ethyl acetate (600 mL×2). The organic phases were combined, dried over anhydrous Na2SO4 and volatiles were evaporated under reduced pressure to yield a pale yellow liquid which was purified through silica gel (230-400) column (5% ethyl acetate in petroleum ether) to give product as a pale yellow liquid 25 g (68.5%).

Workup

  1. temperatureThe reaction mixture was re-cooled to −78° C.
  2. stirringstirred for 15 min
  3. stirringstirred for 1 h
  4. stirringcontinued stirring at −78° C. for 2 h
  5. customto reach room temperature
  6. stirringcontinued stirring over a period of 16 h
  7. customThe resulting reaction mixture
  8. customwas quenched with saturated NH4Cl (1.0 L) at 0° C.
  9. extractionthe reaction mixture was extracted with ethyl acetate (600 mL×2)
  10. dry with materialdried over anhydrous Na2SO4 and volatiles
  11. customwere evaporated under reduced pressure
  12. customto yield a pale yellow liquid which
  13. customwas purified through silica gel (230-400) column (5% ethyl acetate in petroleum ether)

Sources & evidence

ORD record
ord-902e56be9133404296c2cf8f8a955b09
Source dataset
uspto-grants-2014_01
Patent number
US08623897B2

Reaction notes

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